Vibrational Energy Relaxation: A Benchmark for Mixed Quantum–Classical Methods

Jain, Amber; Subotnik, Joseph E.

doi:10.1021/acs.jpca.7b09018

Cited by 34 publications

(40 citation statements)

References 78 publications

(126 reference statements)

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“…The dependence of the accuracy of the MM-SQC dynamics on the Hamiltonian was also discussed by Subotnik and coworkers 55,56 . In fact, the deviation of the MM-SQC 19 results with respect to the ML-MCTDH ones is fully due to the improper treatment of the fast bath modes classically.…”

Section: Symmetric Site-exciton Modelsmentioning

confidence: 86%

Performance evaluation of the symmetrical quasi-classical dynamics method based on Meyer-Miller mapping Hamiltonian in the treatment of site-exciton models

Xie

Zheng

Lan

2018

The Journal of Chemical Physics

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The symmetrical quasi-classical dynamics method based on the Meyer-Miller mapping Hamiltonian (MM-SQC) shows the great potential in the treatment of the nonadiabatic dynamics of complex systems. We performed the comprehensive benchmark calculations to evaluate the performance of the MM-SQC method in various site-exciton models with respect to the accurate results of quantum dynamics method multilayer multiconfigurational time-dependent Hartree (ML-MCTDH). The parameters of the site-exciton models are chosen to represent a few of prototypes used 2 in the description of photoinduced excitonic dynamics processes in photoharvesting systems and organic solar cells, which include the rather board situations with the fast or slow bath and different system-bath couplings. When the characteristic frequency of the bath is low, the MM-SQC method performs extremely well, and it gives almost the identical results to those of ML-MCTDH. When the fast bath is considered, the deviations exist between the MM-SQC and ML-MCTDH results if the high-frequency bath modes are improperly treated by the classical manner. When the so-called adiabatic renormalization was employed to construct the reduced Hamiltonian by freezing high-frequency modes, the MM-SQC dynamics can give the results comparable to the ML-MCTDH ones. Thus, the MM-SQC method itself provide reasonable results in all test site-exciton models, while the proper treatments of the bath modes must be employed. The possible dependence of the MM-SQC dynamics on the different initial sampling methods for the nuclear degrees of freedom is also discussed.3

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Section: Symmetric Site-exciton Modelsmentioning

confidence: 86%

Performance evaluation of the symmetrical quasi-classical dynamics method based on Meyer-Miller mapping Hamiltonian in the treatment of site-exciton models

Xie

Zheng

Lan

2018

The Journal of Chemical Physics

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“…Insights into several aspects of the IVR dynamics have been obtained over the past few decades with novel experimental [24][25][26][27] and theoretical approaches [3,5,6,[28][29][30][31][32][33][34][35]. These studies have brought out the utility of approximately conserved quantities called polyads, emphasized the importance of local density of states coupled to the initial state of interest, and the crucial role * srihari@iitk.ac.in played by various anharmonic resonances at a given energy of interest.…”

Section: Introductionmentioning

confidence: 99%

Relevance of the Resonance Junctions on the Arnold Web to Dynamical Tunneling and Eigenstate Delocalization

Karmakar

Keshavamurthy

2018

J. Phys. Chem. A

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In this work we study the competition and correspondence between the classical and quantum routes to intramolecular vibrational energy redistribution (IVR) in a three degrees of freedom model effective Hamiltonian. Specifically, we focus on the classical and the quantum dynamics near the resonance junctions on the Arnold web that are formed by intersection of independent resonances. The regime of interest models the IVR dynamics from highly excited initial states near dissociation thresholds of molecular systems wherein both classical and purely quantum, involving dynamical tunneling, routes to IVR coexist. In the vicinity of a resonance junction classical chaos is inevitably present and hence one expects the quantum IVR pathways to have a strong classical component as well. We show that with increasing resonant coupling strengths the classical component of IVR leads to a transition from coherent dynamical tunneling to incoherent dynamical tunneling. Furthermore, we establish that the quantum IVR dynamics can be predicted based on the structures on the classical Arnold web. In addition, we investigate the nature of the highly excited eigenstates in order to identify the quantum signatures of the multiplicity-2 junctions. For the parameter regimes studies herein, by projecting the eigenstates onto the Arnold web, we find that eigenstates in the vicinity of the junctions are primarily delocalized due to dynamical tunneling.

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“…We also anticipate applications of the method to multi-level (i.e., beyond two levels) subsystems with more complex environments. Finally, one could consider applying other mixed quantum-classical and semiclassical methods, such as those previously used in the study of vibrational energy transfer in condensed phases [67][68][69], to nonequilibrium heat transfer problems.…”

Section: Discussionmentioning

confidence: 99%

Heat transfer statistics in mixed quantum-classical systems

Liu

Hsieh

Segal

et al. 2018

The Journal of Chemical Physics

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The modelling of quantum heat transfer processes at the nanoscale is crucial for the development of energy harvesting and molecular electronics devices. Herein, we adopt a mixed quantum-classical description of a device, in which the open subsystem of interest is treated quantum mechanically and the surrounding heat baths are treated in a classical-like fashion. By introducing such a mixed quantum-classical description of the composite system, one is able to study the heat transfer between the subsystem and bath from a closed system point of view, thereby avoiding simplifying assumptions related to the bath time scale and subsystem-bath coupling strength. In particular, we adopt the full counting statistics approach to derive a general expression for the moment generating function of heat in systems whose dynamics are described by the quantum-classical Liouville equation (QCLE). From this expression, one can deduce expressions for the dynamics of the average heat and heat current, which may be evaluated using numerical simulations. Due to the approximate nature of the QCLE, we also find that the steady state fluctuation symmetry holds up to order for systems whose subsystembath couplings and baths go beyond bilinear and harmonic, respectively. To demonstrate the approach, we consider the nonequilibrium spin boson model and simulate its time-dependent average heat and heat current under various conditions.

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Vibrational Energy Relaxation: A Benchmark for Mixed Quantum–Classical Methods

Cited by 34 publications

References 78 publications

Performance evaluation of the symmetrical quasi-classical dynamics method based on Meyer-Miller mapping Hamiltonian in the treatment of site-exciton models

Performance evaluation of the symmetrical quasi-classical dynamics method based on Meyer-Miller mapping Hamiltonian in the treatment of site-exciton models

Relevance of the Resonance Junctions on the Arnold Web to Dynamical Tunneling and Eigenstate Delocalization

Heat transfer statistics in mixed quantum-classical systems

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